Journal of Geosciences, 68 (2023), 139–162

DOI: 10.3190/jgeosci.371

Original paper

Mineralogical and geochemical studies of Cu–Bi–Ag±W ores from
Janjevo (Kosovo): Insights into the Bi sulfosalt mineralogy and the
distribution of bismuth in base metal sulfides
Sławomir MEDERSKI1*, Jaroslav PRŠEK1, Joanna KOŁODZIEJCZYK1, Konrad KLUZA1, Vasilios MELFOS2, Katarzyna ADAMEK1, Dimitrina DIMITROVA3
1

Faculty of Geology, Geophysics and Environmental Protection, AGH UST, University of Science and Technology, 30 Mickiewicz Av.,
30-059 Kraków, Poland; mederski@agh.edu.pl2
Department of Mineralogy, Petrology and Economic Geology, Faculty of Geology, Aristotle University of Thessaloniki,
Thessaloniki 54124, Greece
3
Geological Institute, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria* Corresponding author
This work presents a mineralogical and geochemical study of Cu–Bi–Ag ± W ores from Janjevo in the Trepça Mineral
Belt in Kosovo. This locality indicates a new type of Bi–Cu ± Au mineralization within the Kizhnica–Hajvalia–Badovc
ore field, including Cu–Bi ± Ag ± As sulfosalts paragenesis previously not described in Kosovo and in this part of the
Vardar Zone. Chemical composition of Bi–Pb ± Cu ±Ag and Cu–Bi ± Ag ± As sulfosalts, sulfides, and associated minerals, as well as their paragenetic relationships and the distribution of minor and trace elements in main ore minerals, arediscussed based on microscopy, microprobe, and laser ablation inductively coupled plasma mass spectrometry studies.
The Cu–Bi–Ag ± W hydrothermal mineralization in Janjevo was formed during four stages: (1) Early base metal stage,(2) Bismuth stage, (3) Main stage, and (4) Late stage. The Early base metal stage is represented by pyrite, sphalerite I,
chalcopyrite I, galena I, bournonite I, tetrahedrite I, siderite, and quartz. The Bismuth stage includes arsenopyrite I,
löllingite, native bismuth, galena II, chalcopyrite II, tetrahedrite II, quartz, siderite, and Bi–Pb ± Cu ± Ag sulfosalts:
bismuthinite, aikinite, krupkaite, cosalite, and gustavite. The Main stage is represented by chalcopyrite III, tetrahedrite
group minerals (tetrahedrite and tennantite) III, galena III, sphalerite II, arsenopyrite II, bournonite II, and siderite.
The Cu–Bi ± Ag ± As sulfosalts (pearceite, cupropearceite, wittichenite, and an unknown phase: AgCuBiS3) associatedwith galena IV, siderite, and quartz were formed in the final low-temperature Late stage. The application of GGIMFis
geothermometry on sphalerite gives the following sphalerite precipitation temperatures: 220–272 °C for sphalerite I and
160–190 °C for sphalerite II. Presented results show that in addition to numerous Bi sulfosalts in Janjevo Cu–Bi–Ag ± W
ores, bismuth has been incorporated into base metal sulfides, as well as arsenopyrite. The main carrier of bismuth isarsenopyrite I, which has started the crystallization of the bismuth stage.
Keywords: bismuth, sulfosalts, tetrahedrite group minerals, AgCuBiS3, LA-ICP-MS
Received: 4 October 2022; accepted: 13 February 2023; handling editor: J. Sejkora
The online version of this article (doi: 10.3190/jgeosci.371) contains supplementary electronic material.

1. Introduction
The Janjevo Cu–Bi–Ag ± W mineralization is located incentral Kosovo, about 10 km SE of the capital Prishtina(Fig. 1). It is situated in the southern part of the Trepça
Mineral Belt (TMB), which is part of a major metallogenic zone, the Serbo-Macedonian metallogenic province(SMMP), part of the Western Tethyan metallogenic belt
(Janković 1997; Borojević Šoštarić et al. 2012; Baker
2019). The SMMP was formed during the late Oligocene to early Miocene post-collision extension and theassociated intermediate to felsic magmatic activity withmagmas of high-K, calc-alkaline to shoshonitic composition (Borojević Šoštarić et al. 2012; Siron et al. 2016).
The SMMP is predominantly known for the occurrenceof many Pb-Zn-Ag deposits (Strmić Palinkaš et al. 2013;
Radosavljević et al. 2013; Kołodziejczyk et al. 2016a;
Siron et al. 2016; Stojanović et al. 2018).
Polymetallic Pb–Zn–Ag deposits occur, for example,
in the Kizhnica–Hajvalia–Badovc (KHB) ore field, which
also includes the Janjevo Cu–Bi–Ag ± W occurrence located in the eastern part of the ore field (Fig. 2). There
are three major Pb–Zn–Ag deposits documented in thisore field. These deposits were mined in the 20th century.
However, mining in the KHB ore field dates to Romantimes, and many small-scale mining works are observedin the entire area. Short adits, dumps, and remnants ofmining infrastructure in the eastern part of the KHB ore
field suggest mining activity focused on different metals(mainly copper). Mineral occurrences in the eastern partwww.jgeosci.org

Sławomir Mederski, Jaroslav Pršek, Joanna Kołodziejczyk, Konrad Kluza, Vasilios Melfos, Katarzyna Adamek, Dimitrina Dimitrova

21°E
SerbiaII
Belo Brdo

Montenegro

42°N
Bulgariae
rbo anon
Se doni an
rZ
ce pe
rda
Va
Ma do ifos
Rh MasB
TM

BiH

Adriatic Sea

Crnac

I

de lt
ari beDin nidelle
He

KosovoIII

North
Albania Macedonia
100 kmGreeceStan Terg
Mitrovica
Batlava
Miocene sediments
Tertiary volcanics & volcanoclatics
Jurassic & Cretaceous sediments
Ultramafic rocks

Prishtina
Hajvalia

Paleozoic & Triassic metasediments
FaultsKizhnica

Janjevo

Novo Brdo/
ArtanaMine
Mineralization occurrence

10 km

Fig. 1 – Simplified geological map of Vardar Zone and Trepça Mineral Belt (TMB) (modified after Hyseni et al. 2010; Strmić Palinkaš et al.
2013), the dashed-line square shows the Kizhnica–Hajvalia–Badovc ore field presented in Fig. 2. I = Batlava–Artana Zone, II = Belo Brdo–Stan
Terg–Hajvalia Zone, III = Crnac Zone.

of the KHB ore field are associated with the Bi–Cu ± Au
metallogenic zone and their proximity to intrusive rocks
have been described by Mederski et al. (2021a) (Fig. 2).
This work presents detailed mineralogical and geochemical characteristics of a newly discovered hydrothermal Cu–Bi–Ag ± W mineralization in Janjevo,
Kosovo. The chemical composition of Bi–Pb ± Cu ± Ag
and Cu–Bi ± Ag ± As sulfosalts, sulfides, and associatedminerals, as well as their paragenetic relationships andthe distribution of minor and trace elements in main ore
minerals, are presented. Special attention is given to
the mineralogy of Bi-sulfosalts and the evolution anddistribution of bismuth in the main ore minerals in the
Cu–Bi–Ag ± W ores from Janjevo.

2. Geological setting
The Janjevo area is part of the NW–SE trending Vardar
Zone, which is bounded by the Dinarides, the Drina–
Ivanjica Terrain, and the Pelagonian Zone to the west,
140

and the Serbo–Macedonian Massif to the east. The Vardar
Zone is composed of Paleozoic–Triassic metamorphic
rocks, Jurassic ophiolite complex (serpentinite and gabbro with minor sedimentary rocks), Jurassic and Cretaceous sedimentary complex (series of flysch, carbonate
rocks, volcanic and volcanoclastic rocks), and Tertiary
andesites, trachytes, latites, and felsic pyroclastic rocks(Janković 1995; Cvetković et al. 2004; Elezaj 2009;
Borojević Šoštarić et al. 2012; Strmić Palinkaš et al.
2013) (Fig. 1). The Oligocene-Miocene polymetallic mineralization extends along the so-called Trepça Mineral
Belt (TMB), which is related to the post-collisional calcalkaline to shoshonitic magmatic activity accompanied bywidespread hydrothermal activity (Janković 1995; Hyseni
et al. 2010). Mineralization within the TMB is controlled
by three NNW-trending regional fault zones: (I) Batlava–
Artana Zone, (II) Belo Brdo–Stan Terg–Hajvalia Zone,
and (III) Crnac Zone (Hyseni et al. 2010) (Fig. 1). The
TMB region is dominated by hydrothermal Pb–Zn–Ag
deposits: skarns, carbonate replacements, veins, breccias, veinlets, and disseminations in altered rocks such asMineralogical and geochemical studies of Cu–Bi–Ag±W ores from Janjevo (Kosovo)

Jurassic & Cretaceous sediments
Fig. 2 – Simplified geological map of
the Kizhnica–Hajvalia–Badovc ore field.
Abbreviations: I = Hajvalia–Badovc Tectonic Zone; II = Kizhnica Tectonic Zone;
III = Okosnica Tectonic Zone.

Jurassic tectonic mélange & olistoliths

42.59°Ni±N-Sb-Zn nezoPb

and schists), while the Kizhnica Pb–Zn–Ag deposit islistvenites (Hyseni et al. 2010; Borojević Šoštarić et al.
located on the contact between serpentinites and fly2011, 2013; Strmić Palinkaš et al. 2013; Radosavljević
sch series, and forms veins, lenses, and disseminations
et al. 2015; Kołodziejczyk et al. 2015, 2016a, b, 2017;
Mederski et al. 2019, 2021a, b, 2022b).
(Dangić 1985; Kołodziejczyk et al. 2016a). The Badovc
The oldest rocks in the KHB ore field belong to the
Pb–Zn–Ag deposit occurs in the form of banded-veins,
Paleozoic–Triassic metasedimentary complex, composed
veinlets, and disseminations within the listvenites (Medof schists and marbles, which occur in the western part
erski et al. 2019, 2021b, 2022b). In the southern part ofof the ore field (Fig. 2). In the central part of the area, an
the area, there is a distal Sb–As–Tl–Hg zone (Fig. 2),
ultramafic complex of Triassic–Jurassic age is exposed,
where a low-temperature sediment-hosted As–Sb–
which is represented by gabbro, serpentinized basalts,
Tl–Pb ± Hg ± Au mineralization occurs within Triassic
peridotites, and in places is altered by later hydrothermal
marbles in Janjevo (Mederski et al. 2022a, 2022b). Minfluids that formed carbonate listvenites (Mederski et al.
eralization associated with the Bi–Cu ± Au zone is known
2019, 2021b). In the southern part of the area, there isfrom a few minor occurrences in the eastern part of thea Jurassic mélange series with olistoliths, composed of
KHB ore field. Epithermal Cu–Bi veinlets and veinlets
various metamorphosed rocks in the greenschist facies,
with Bi sulfosalts are observed within the Kizhnica anprimarily sedimentary and mafic rocks. The eastern part
desite (Mederski et al. 2021a). In the NE part of the area,of the area contains terrigenous rocks of Jurassic–CreBi–Au–Cu–Te mineralization with Bi sulfosalts hosted
taceous age. The flysch series
21.24°E
is represented by fining-upward
sequences of conglomerates,
Hajvalia
silty-calcareous units, greywacke,
sandy and silty lithologies, and Pb-Zn-Ag
I
calcareous sandstone to pebble
conglomerates (Buerger and GiII
roux 2016). The youngest andIIImost extensive units are OliKizhnica
gocene–Miocene volcanic and
Bi-Au-Cu-Te
volcanoclastic rocks. Intrusive
dikes and sills are represented
by a hornblende-biotite porphyry
Kizhnica
andesite and a feldspar porphyry
Kizhnica
Pb-Zn-Ag
andesite (Buerger and Giroux
andesite quarry
Badovc2016).
Pb-Zn-Ag
The Kizhnica–Hajvalia–Badovc (KHB) ore field showsa metallogenic zonation describedby Mederski et al. (2021a) that
may be related to a concealed
porphyry system (Fig. 2). The
Janjevocentral and western parts are
Sb
Cu-Bi-Ag(W)-A
characterized by the presencezo s-Tof a Pb–Zn–Sb ± Ni zone, andJanjevone l-H
there are major documented Pb–
g
As-Sb-TlBi-Cu±Au
Zn–Ag deposits in the KHB ore
1 km
zone
field, including Hajvalia, Badovc, and Kizhnica (Fig. 2). The
Hajvalia carbonate replacement
FaultsMiocene sediments
Pb–Zn–Ag deposit is hosted in
MineTertiary volcanics & volcanoclatics
Paleozoic formations (marbles
Mineralization
occurrence

Research area

Ultramafic rocks
Paleozoic & Triassic metasediments
141

Sławomir Mederski, Jaroslav Pršek, Joanna Kołodziejczyk, Konrad Kluza, Vasilios Melfos, Katarzyna Adamek, Dimitrina Dimitrova

(a)

Apy

FeOOH

(b)

(c)

Sd
Apy
Sd
Sd

Gn + Ttr

Ccp + Ttr
5 cm

(d)

Qz + Gn
2 cm

(e)

Py

1 cm

(f)

Ccp
Gn + Bi ss

Qz
Feb

Qz

Qz + Gn
5 cm

2 cm

2 mm

Fig. 3 – Representative photographs of the Cu–Bi–Ag±W ores from Janjevo. a–d – Polymetallic siderite ore with arsenopyrite, tetrahedrite, galena, chalcopyrite, and quartz. e – Quartz ore with galena, chalcopyrite, and Bi sulfosalts. f – Euhedral wolframite (ferberite) crystal from quartz
druse. Apy – arsenopyrite, Bi ss – bismuth sulfosalts, Ccp – chalcopyrite, Feb – ferberite, FeOOH – Fe hydroxides, Gn – galena, Py – pyrite,
Sd – siderite, Qz – quartz, Ttr – tetrahedrite.

by hornfels between flysch and andesite intrusions waspreviously described by Mederski et al. (2021a). Similar
mineralization is documented in the Slivovo Au–Ag
deposit east of the KHB ore field (Buerger and Giroux
2016). In the SE part of the KHB ore field, the Janjevo
Cu–Bi–Ag ± W mineralization occurs at the contact between the flysch series and andesites (Westner 2017;
Mederski et al. 2021c).

3. Locality and investigated material
Material for the study was collected from small historicalwaste piles on one of the hills between the Janjevo village
and the Kizhnica andesite quarry. Mineralized ore samples with Cu–Bi–Ag ± W association were found close
to the entrance of a backfilled adit. The GPS coordinatesof the sampling site are 42°34'57.92"N, 21°15'1.54"E.
Outcrops with altered andesites have been observed in
the close vicinity. In addition, flysch series rocks were
noticed at the entrance of the drainage adit, which is inaccessible due to the clenching of siltstone rocks. The orefrom Janjevo is coarse-grained, composed primarily ofsiderite (Fig. 3a–b), which is replaced by iron hydroxides
due to weathering. Within the siderite ores are numerous
polymineralic aggregates of up to several cm in size,
composed of arsenopyrite, pyrite, chalcopyrite, galena,and tetrahedrite (Fig. 3a–d). In addition, there are bandedsiderite-arsenopyrite ores (Fig. 3c), as well as quartz ores
142

with aggregates of galena, chalcopyrite, and Bi sulfosalts(Fig. 3e). Tiny wolframite crystals up to a few mm in size
were observed in the quartz druses (Fig. 3f).

4. Methods
Samples from the Janjevo Cu–Bi–Ag ± W locality were
examined macroscopically, and based on visual evaluation, a number of 27 thin and polished sections wereprepared for mineralogical research. Mineral assemblages
and textural relationships were studied using reflected andtransmitted light microscopy. The quantitative element
composition of sulfides, sulfosalts, and other associatedminerals was obtained in 10 samples representing major
types of mineralization using electron probe microanalysis (EPMA). Trace element composition of selectedminerals (pyrite, sphalerite, chalcopyrite, arsenopyrite,
and tetrahedrite group minerals) was determined by laser
ablation inductively coupled plasma mass spectrometry(LA-ICP-MS) in four samples.
Quantitative chemical analyses of sulfides, sulfosalts,
and other associated minerals were performed on a JEOL
Super Probe 8230 electron microprobe (Kraków, Poland:Laboratory of Critical Elements at Faculty of Geology,
Geophysics, and Environmental Protection, AGH-UST),
operating in the wavelength-dispersive (WDS) mode
(20 kV [exception wolframite: 15 kV], 20 nA [exception pearceite–cupropearceite: 10 nA], and 1–2 μm wide

Mineralogical and geochemical studies of Cu–Bi–Ag±W ores from Janjevo (Kosovo)beam). The following standards, X-ray lines, and detection limits (in wt. %) for the minerals measured (pyrite,
arsenopyrite, löllingite, tetrahedrite group minerals, Bi
and Ag sulfosalts, galena, wolframite, and siderite) aresummarized in Tab. S1 (ESM 1). Microprobe microanalyses were conducted for the determination of iron, copper, and zinc contents used as internal standards during
LA-ICP-MS analyses for pyrite (Fe), chalcopyrite (Fe),arsenopyrite (Fe), tetrahedrite group minerals (Cu), andsphalerite (Zn).
Trace element concentrations in pyrite, sphalerite,
chalcopyrite, arsenopyrite, and tetrahedrite group minerals were measured using a PerkinElmer ELAN DRC-e
ICP mass spectrometer combined with a New Wave
UP193-FX excimer laser ablation system at the Geological Institute, Bulgarian Academy of Sciences, Sofia,
Bulgaria. The ablation was conducted in He medium. To
maximize sensitivity, the ICP-MS was optimized daily
concerning the oxide production rate of ThO/Th (0.5 %).
Operating conditions of the laser system include a 6 Hz
repetition rate; 20 to 35 μm spot size; and energy density
on analyzed minerals and standards of 3.3–3.4 J/cm2(at 35 μm spot), 3.1 J/cm2 (at 25 μm spot), and 2.9–3.0
J/cm2 (at 20 μm spot). The nebulizer gas flow rate was 0.8
L/min, while auxiliary and make-up gas flow rates were0.92 L/min. The analysis time was 100 s (background:
40 s, laser-on the sample: 60 s). The acquisition dwells
time was set to 0.02 s for 71Ga, 74Ge, 107Ag, 125Te, 202Hg,
205
Tl; to 0.03 s for 115In, 118Sn; to 0.04 s for 197Au, and0.01 s for all other monitored isotope masses – 34S, 49Ti,
51
V, 53Cr, 55Mn, 57Fe, 59Co, 60Ni, 65Cu, 66Zn, 71Ga, 74Ge,
75
As, 82Se, 95Mo, 107Ag, 111Cd, 115In, 118Sn, 121Sb, 125Te,
181
Ta, 182W, 197Au, 202Hg, 203Tl, 208Pb, and 209Bi. Targetedareas in the polished sections were predefined to avoid
obvious mineral inclusions. Repeated external standardization was conducted by analyzing NIST SRM 610 glass
standard and the USGS Mass 1 sulfide standard. Data
reduction was made using SILLS software (Guillong et al.
2008). During data reduction, peak-shaped fluctuations of
the intensity signal of some isotopes were investigated to
exclude the influence of other minerals on the chemicalcomposition of the studied minerals. Limits of detection
for each isotope mass are determined for every analysis
and may differ.

5. Results

5.1. Paragenetic sequence
The Cu–Bi–Ag ± W hydrothermal mineralization in Janjevo was formed during four main stages (Fig. 4): (1) Earlybase metal stage, (2) Bismuth stage, (3) Main stage, and(4) Late stage. Each stage contains different generationsof sphalerite, chalcopyrite, galena, bournonite, and tetrahedrite group minerals, that have been distinguishedbased on textural features and the geochemistry of traceelements. The first stage is represented by sulfides: pyrite,
sphalerite I, chalcopyrite I, galena I, and sulfosalts: bournonite I, and tetrahedrite I. The main gangue minerals are
siderite and quartz. The second Bi-dominated stage begins with the crystallization of arsenopyrite and traces oflöllingite and native bismuth. Numerous Bi–Pb ± Cu ± Ag
sulfosalts represented by bismuthinite, aikinite, krupkaite,
cosalite, and gustavite were crystallized subsequently
with quartz, galena II, chalcopyrite II, and tetrahedrite II.
The main productive stage of precipitation includes chalcopyrite III, tetrahedrite group minerals (tetrahedrite andtennantite) III, galena III, sphalerite II, arsenopyrite II,bournonite II, and siderite. Texture observations suggestthat the Cu–Bi ± Ag ± As sulfosalts (pearceite, cupropearceite, wittichenite, and an unknown phase: AgCuBiS3)
associated with galena IV, siderite, and quartz, wereformed in the final low-temperature Late stage in Janjevo.

5.2. Mineralogy and textures
EPM analyses of sulfides, sulfarsenides, diarsenides, andassociated minerals are presented in Tab. S2 (ESM 2),
while sulfosalts analyses are presented in Tab. S3(ESM 3).

5.2.1. Sulfides
Pyrite is a minor sulfide in ores from Janjevo and crystallized during the first early base metal stage (Fig. 4).
It forms euhedral crystals up to 200 μm in size or larger
subhedral aggregates up to 600 μm (Fig. 5a). Pyrite crystals often host numerous inclusions of younger galena,arsenopyrite, or sphalerite. In addition, younger sulfides
very often overgrow pyrite crystals (Fig. 5a). The Formula of pyrite from Janjevo can be expressed as (Fe0.97–1.00
Ni0.00–0.03)Σ1.00(S1.94–2.05As0.00–0.05)1.98–2.05.
Sphalerite is a common sulfide at Janjevo and occurs in two generations. Sphalerite I forms irregular aggregates up to 2 mm in size that crystallized during thefirst early base metal stage (Fig. 5b, c). This sphalerite
contains numerous chalcopyrite exsolutions (chalcopyrite I) (Fig. 5b) at the rims and is overgrown by younger
galena I. It is characterized by high iron concentration (Feup to 0.19 apfu), with iron-dependent oscillatory zonation
visible in BSE images (Fig. 5c). A generalized formulafor sphalerite I is (Zn0.80–0.98Fe0.02–0.19)Σ1.00S0.99–1.05. Sphalerite II crystallized during the third, main stage (Fig. 4),
forming aggregates of up to 500 mm in size. It occurs
mainly in association with chalcopyrite III (Fig. 5d), andis characterized by significantly lower iron concentration (up to 0.03 apfu), compared with sphalerite I. The
143

Sławomir Mederski, Jaroslav Pršek, Joanna Kołodziejczyk, Konrad Kluza, Vasilios Melfos, Katarzyna Adamek, Dimitrina Dimitrova

Mineral

Stage(1) Early basemetal stage(2) Bismuth stage(3) Main stage(4) Late stage

Siderite
PyriteSphalerite
Chalcopyrite
GalenaBournonite
Tetrahedrite-Tennantite

Sph I

Sph II270-220°C

Ccp I

Ccp II
Gn I

Gn II

190-160°C

Ccp IIIGn III

Bnn I

Gn IV

Bnn II
Ttr II

Ttr I

Ttr-Tnt III

QuartzArsenopyrite

Apy I

Apy II

Löllingite
Native Bi
Bismuthinite
Cosalite
Gustavite
Krupkaite
Aikinite
Pearceite-Cupropearceite

Wittichenite
Unknown phase CuAgBiS3
Fig. 4 – Formation stages and paragenetic sequence of Cu–Bi–Ag±W mineralization from the Janjevo. The dashed lines indicate specific generations of minerals that were measured by the LA-ICP-MS technique.

formula of sphalerite II can be expressed as (Zn0.95–0.99
Fe0.01–0.03Ga0.00–0.01)Σ1.00S0.97–1.02.
Chalcopyrite is the most common sulfide in the studied samples, and occurs in three stages, chalcopyrite I, II
and III. Chalcopyrite I occurs as exsolutions and minor
inclusions in sphalerite I (Fig. 5b). In contrast, chalcopyrite II co-crystallized with aikinite (Fig. 6h). The mostabundant generation is chalcopyrite III that formed in themain precipitation stage (Fig. 4). It is found in aggregateswith tetrahedrite, galena, and sphalerite up to several cm
in size (Fig. 5d–f). Occasionally it forms euhedral crys144

tals at the rims of the aggregates. The chemical compositions of all generations of chalcopyrite correspond almost
to the ideal stoichiometry of this mineral phase with theformula: (Cu0.98–0.99Fe01.01–1.02)Σ2.00S1.97–2.06.
Galena is widespread in the ore and is found in all
four stages of precipitation, and occurs in four generations, galena I, II, III, and IV (Fig. 4). Galena I overgrows
sphalerite I, but also forms larger aggregates up to 2 μm
(Fig. 5b–c). In addition, tetrahedrite and bournonite
inclusions are observed within galena I. Galena II isassociated with Bi sulfosalts: bismuthinite and cosalite

Mineralogical and geochemical studies of Cu–Bi–Ag±W ores from Janjevo (Kosovo)

(a)

(c)

(b)

(e)

(d)

500 μm(f)

500 μm(h)(g)

500 μm200 μm200 μm(i)

500 μm(k)(j)

200 μm200 μm

100 μm

100 μm(l)

200 μm

100 μmFig. 5 – Reflected-light photomicrographs (a–b, d–i, k) and back-scattered electron (BSE) images (c, j, l) of Cu–Bi–Ag ± W mineralization from the
Janjevo. a – Euhedral pyrite crystal is overgrown by younger galena and arsenopyrite II, siderite. b – Aggregates of sphalerite I with exsolutionsof chalcopyrite I have overgrown by arsenopyrite and galena, siderite. c – Oscillatory zonation in sphalerite I related to variable Fe content, overgrown by galena I and tetrahedrite I, quartz. d – Typical coarse-crystalline aggregates composed of chalcopyrite III, sphalerite II and tetrahedritetennantite III overgrown by arsenopyrite II, quartz. e – Arsenopyrite I associated with aggregates composed of chalcopyrite III and galena III,
quartz. f – Typical polymineralic aggregates chalcopyrite III–tetrahedrite–tennantite III–galena III overgrown by arsenopyrite II, siderite, and quartz.
g – Coarse-crystalline galena III with tetrahedrite-tennantite III and arsenopyrite II. h – Galena III with tetrahedrite-tennantite III and arsenopyrite
II filling the cavity between euhedral crystals of siderite and quartz, chalcopyrite III. i – Disintegration textures of arsenopyrite I–löllingite aggregates with visible droplets of native bismuth. j – Disintegration textures of arsenopyrite I–löllingite aggregates with visible droplets of native
bismuth in euhedral löllingite crystals, chalcopyrite III. k – Skeletal aggregates of arsenopyrite II in siderite. l – An elongated euhedral crystal ofarsenopyrite II. Apy – arsenopyrite, Bi – native bismuth, Ccp – chalcopyrite, Gn – galena, Lö – löllingite, Py – pyrite, Qz – quartz, Sd – siderite,
Sp – sphalerite, Tnt – tennantite, Ttr – tetrahedrite.

145

Sławomir Mederski, Jaroslav Pršek, Joanna Kołodziejczyk, Konrad Kluza, Vasilios Melfos, Katarzyna Adamek, Dimitrina Dimitrova(Fig. 5f), and forms aggregates of up to 2 mm. Galena IIshows elevated contents of Bi (up to 0.03 apfu). Galena
III very commonly overgrows chalcopyrite–tetrahedrite
aggregates (Fig. 5f), as well as arsenopyrite I (Fig. 5g–h).
It forms crystals up to 3 mm, which are characterized
by only minor concentrations in Bi (up to 0.01 apfu),
the Formula of galena III can be expressed as (Pb0.97–1.00
Sb0.00–0.02Bi0.00–0.01)Σ1.00S0.96–0.98. The youngest galena IV cocrystallized with Ag minerals: pearceite and wittichenite,
and is characterized by high concentrations of Bi (upto 0.10 apfu) and Ag (up to 0.06 apfu), the formula ofgalena IV can be expressed as (Pb0.78–0.87Bi0.06–0.10Ag0.03–0.06
Cu0.03–0.05Fe0.01–0.02)Σ1.00S0.95–0.96.

5.2.2. Sulfarsenides + diarsenides
Arsenopyrite is the most common ore mineral in the studied samples, and two generations are observed, arsenopyrite I and II (Fig. 4). Arsenopyrite I forms aggregates up
to several mm in size, composed of euhedral arsenopyrite
crystals, very often accompanied by löllingite (Fig. 5i–j).
These aggregates are commonly corroded and are overgrown by the ore minerals of the younger mineralization,
abundant in tetrahedrite, chalcopyrite, and galena. In addition, large aggregates of arsenopyrite I with löllingite
often show the presence of irregular native Bi blebs inside(Fig. 5i–j). The formula of arsenopyrite I can be expressed
as Fe1.00(As0.85–1.01Sb0.00–0.03Bi0.00–0.01)Σ0.88–1.01S0.95–1.06. Arsenopyrite from Janjevo shows elevated Sb concentration
up to 0.03 apfu in arsenopyrite I and II. Arsenopyrite II
postdates all the other sulfides at the main stage, apartfrom galena IV (Fig. 4). It mainly forms characteristic
euhedral crystals (Fig. 5k–l), sometimes growing on older
sulfides (Fig. 5f, h). The formula of arsenopyrite II can be
expressed as Fe1.00(As0.87–0.96Sb0.00–0.03)Σ0.90–0.97S0.95–1.05.
Löllingite co-crystallized with arsenopyrite I andforms euhedral to subhedral crystals up to 100 μm(Fig. 5i–j). There are no isolated crystals of löllingite,
but it always forms aggregates with arsenopyrite I. In
addition, irregular native Bi droplets are observed within
the aggregates (Fig. 5i–j). A generalized formula forlöllingite is Fe1.00(As1.85–1.93S0.01–0.09)Σ1.93–1.99.

5.2.3. Sulfosalts
The tetrahedrite group minerals are widespread andare the most common sulfosalts in the Janjevo ores.
Minerals of this group crystallized during the first threehydrothermal stages (Fig. 4). Tetrahedrite I co-crystallized with galena I and bournonite I, and forms irregularaggregates up to 150 μm (Fig. 5c; 6a). According to therecently published nomenclature scheme of minerals of
the tetrahedrite group (Biagioni et al. 2020), tetrahedrite I
is represented by Sb members with mixed Fe and Zn
146

concentrations at the C structural position: tetrahedrite(Fe) predominates, only one analysis can be classified as
tetrahedrite-(Zn) (Fig. 7a–b). In addition, tetrahedrite I
has the highest Ag values of all generations: 0.46–0.97
apfu (Fig. 7c). A generalized formula for tetrahedrite(Fe) (tetrahedrite I generation) based on 16 cations is(Cu 9.02–9.53Ag 0.46–0.95Fe 1.06–1.47Zn 0.50–1.04) Σ=11.95–12.15(Sb 2.09–3.91
As0.08–1.79Bi0.00–0.06)Σ=3.85–4.05S12.74–13.09. Tetrahedrite II occurs
in association with chalcopyrite, aikinite, galena II, andgustavite. All analyses fall on tetrahedrite-(Fe) (Fig.7d),
and a generalized formula for tetrahedrite II based on 16
cations is (Cu9.32–9.61Ag0.37–0.56Fe1.46–1.60Zn0.40–0.63)Σ=11.93–12.01(Sb3.29–3.83As0.12–0.64Bi0.04–0.13)Σ=3.99–4.07S13.08–13.39. Tetrahedrite
II also shows minor enrichment in Ag (up to 0.56 apfu)(Fig. 7c). Tetrahedrite–tennantite III is abundant in theore from Janjevo. It forms sizable irregular aggregatesassociated with chalcopyrite III, sphalerite II, and galena
III, and the aggregates, or euhedral crystals, sometimes
reach up to 1 cm (Fig. 5f–g; 6b). This generation is characterized by significant chemical variability at positions
C (Fe–Zn) (Fig. 7b) as well as D (Sb–As) (Fig. 7a). In
this generation, the four members of the tetrahedrite groupminerals are represented by tetrahedrite-(Fe), tetrahedrite(Zn), tennantite-(Fe), and tennantite-(Zn) (Fig. 7d). The
considerable chemical variability (especially related to Sb–
As substitution) contributes to the significant zonality seenin BSE images: oscillatory (Fig. 6c–e) as well as irregular(Fig. 6e). The presence of the end members of the tetrahedrite group also influences their differentiation by opticalfeatures visible under the microscope in reflected light: stoichiometric tetrahedrite is olive green, while stoichiometrictennantite shows a bluish tint (Fig. 6b). In addition, tetrahedrite–tennantite III shows slight enrichments at the C position: Hg (up to 0.24 apfu), Pb (up to 0.02 apfu), and Mn (upto 0.01 apfu), and at the D position: Bi (up to 0.31 apfu). A
generalized formula for tetrahedrite-tennantite III based on
16 cations is: (Cu9.49–10.04Ag0.04–0.47Fe1.00–1.86Zn0.09–1.05Hg0.00–0.01
Pb0.00–0.01Mn0.00–0.01)Σ=11.92–12.42(Sb1.80–3.95As0.02–1.90Bi0.00–0.31)Σ=3.58–4.08
S 12.52–13.47 for tetrahedrite-(Fe), (Cu 9.49–10.18 Ag 0.02–0.32
Zn 0.99–1.84Fe 0.16–0.99Hg 0.00–0.06Pb 0.00–0.02) Σ=11.85–12.43(Sb 1.79–3.91
As0.12–1.94Bi0.01–0.21)Σ=3.57–4.15S12.71–13.44 for tetrahedrite-(Zn),(Cu9.82–10.10Ag0.01–0.29Fe0.99–1.95Zn0.05–0.96Hg0.00–0.01Pb0.00–0.01)Σ=11.83–12.46(As1.75–4.15Sb0.00–1.79Bi0.00–0.26)Σ=3.54–4.17S12.77–13.55 for tennantite(Fe), and (Cu9.83–10.15Ag0.01–0.12Zn0.99–1.21Fe0.79–1.02Pb0.00–0.01)Σ=11.86–12.17(As2.32–3.98Sb0.14–1.65Bi0.01–0.09)Σ=3.83–4.14S12.71–13.21 for tennantite(Zn).
Sulfosalts of the bismuthinite–aikinite series arecommon in Janjevo paragenesis. Three members of thisseries: bismuthinite, krupkaite, and aikinite were identified (Fig. 8; 9). Precise identification was based on a
calculation of the degree of aikinite substitution (n aik):(Bi3+ + □ ↔ Pb2+ + Cu+) proposed by Topa et al. (2002).
The value of naik was calculated following the scheme:
naik = 25(x + y)/2, where x is the number of Cu atoms andMineralogical and geochemical studies of Cu–Bi–Ag±W ores from Janjevo (Kosovo)

(a)

(c)

(b)

Ttr-Tnt III
Ttr

Tnt
Ttr I
Ccp III

Tnt

Ttr
Gn I 20 μm(d)

Ttr-Tnt III

Ttr-Tnt III

(e)

Apy I

50 μm

200 μm(f) Cos Krp

Ttr-Tnt III

Qz

Tnt-(Fe)
Bin
Tnt
Ttr
200 μm(g)

Ttr-(Fe)
Gn II

(h)

Krp

Apy I
Aik

Cos

Lö

Aik

Ccp IIAik
200 μm(j)

250 μm

(i)

Apy I

Qz

Gn III

500 μm

(k)

Gn II

Aik

Cos

100 μm

Qz

(l)

Aik

Gn II

Qz

100 μm50 μm

Gn IIICos

100 μm

As: ~0.3 apfu
Sb: ~0.6 apfu

Sb: ~0.8 apfu

Bnn II

25 μm

Fig. 6 – Reflected-light photomicrographs (b, g–h) and back-scattered electron (BSE) images (a, c–f, i–l) of sulfosalts from the Janjevo. a – Irregular zonation in tetrahedrite I. b – Tetrahedrite–tennantite III aggregate with chalcopyrite. The difference in optical characteristics between
olive green stoichiometric tetrahedrite and stoichiometric tennantite with a blue tint is visible in reflected light. c – Oscillatory zonation in tetrahedrite–tennantite III aggregates, elongated arsenopyrite I crystals. d – Oscillatory and irregular zonation in a euhedral tetrahedrite–tennantite
crystal III. e – Oscillatory and irregular zonation in a euhedral tetrahedrite–tennantite crystal III. f – In quartz ore, a polymineralic aggregate
composed of bismuthinite, krupkaite, cosalite, and galena II. g – Elongated aikinite, cosalite, and krupkaite crystals fill the void between quartz
crystals. h – Aikinite crystals are associated with chalcopyrite II, galena II, and arsenopyrite I. i – Elongated aikinite aggregates in association
with arsenopyrite I and löllingite. j – Aikinite–cosalite aggregates in association with galena II and quartz. k – Elongated aikinite–cosalite crystals
accompanied by galena II and quartz. l – A bournonite II crystal with an outer rim enriched in arsenic, accompanied by galena III. Aik – aikinite,
Apy – arsenopyrite, Bin – bismuthinite, Bnn – bournonite, Ccp – chalcopyrite, Cos – cosalite, Gn – galena, Krp – krupkaite, Lö – löllingite,
Qz – quartz, Tnt – tennantite, Ttr – tetrahedrite.

147

Sławomir Mederski, Jaroslav Pršek, Joanna Kołodziejczyk, Konrad Kluza, Vasilios Melfos, Katarzyna Adamek, Dimitrina Dimitrova

2

(a)

4

(b)
1.6

tetrahedriteZn [apfu]

Sb [apfu]

3

2

1.2

0.8

tennantite

1

Tetrahedrite I
Tetrahedrite II
Tetrahedrite-Tennantite III

0.4

0

0
0

1

2
As [apfu]

3

0

4

1

0.4

0.8
1.2
Fe [apfu]

1.6

1

(c)

(d)
0.8

Sb/(Sb+As) [apfu]

Ag [apfu]

0.8

0.6

0.4

0.2

0

0.6

ttr-(Fe)ttr-(Zn)tnt-(Fe)tnt-(Zn)

0.4

0.2

9

9.5
Cu [apfu]

10

0

0

0.2
0.4
0.6
0.8
Zn/(Zn+Fe+Hg) [apfu]

y is the number of Pb atoms in the formulae, based on
the sum Ag + Bi + Sb + Fe + As + (Pb + Cu)/2 = 8 atoms.
Bismuthinite is rare in the studied samples and is theoldest mineral of the bismuthinite-aikinite series in the
Janjevo ores. It occurs only in quartz in association withother Bi sulfosalts (aikinite, krupkaite, cosalite), which
overgrow bismuthinite crystals up to 400 μm in size
(Fig. 6f). The degree of aikinite type substitution (naik) inbismuthinite from Janjevo is 0.24–6.80 (Tab. S3; Fig. 8).
The empirical formula for studied bismuthinite can be
expressed as (Bi7.70–7.98Pb0.00–0.31Cu0.00–0.31Fe0.00–0.01As0.00–0.02
Sb0.01)Σ8.01–8.27S11.94–12.31.
Krupkaite is rare in the studied samples and wasfound in aggregates up to 30 μm in size. It forms intergrowths with bismuthinite and cosalite (Fig. 6f,g), with gustavite, or tiny inclusions in quartz. The
degree of aikinite type substitution (naik) in krupkaitefrom Janjevo is 50.14–56.54 (Tab. S3; Fig. 8). The
empirical formula for studied krupkaite can be exp r e s s e d a s ( C u 2.10–2.26P b 1.92–2.16F e 0.01–0.10A g 0.00–0.02
Bi5.66–5.87Sb0.01–0.11As0.00–0.02)Σ10.01–10.17S11.54–12.19. It contains
traces of Sb (up to 0.11 apfu).
Aikinite is the most common member of bismuthinite–aikinite series occurring in the ore from Janjevo. It forms
elongated crystals up to 400 μm in size and is spatially
148

2

1

Fig. 7 – Compositional relationships in
the tetrahedrite group minerals (TGM)from the Janjevo. a – Sb vs. As binary
plot (apfu). b – Zn vs. Fe binary plot
(apfu). c – Ag vs. Cu binary plot (apfu).
d – Sb/(Sb+As) vs. Zn/(Zn + Fe + Hg)
binary plot (apfu) after Biagioni et al.
(2020).

associated with other Bi sulfosalts (bismuthinite, cosalite,
and krupkaite) and sulfides (chalcopyrite II and galena II)(Fig. 6g–k). The empirical formula for studied aikinite
can be expressed as (Cu3.00–3.93Pb3.21–3.89Fe0.00–0.28Ag0.00–0.04
Bi 4.02–4.78Sb 0.00–0.08As 0.00–0.05) Σ11.16-11.88S 10.60–12.40, while thedegree of aikinite type substitution is 82.33–99.29 (Tab.
S3; Fig. 8). It contains traces of Sb (up to 0.08 apfu) andFe (up to 0.28 apfu).
Cosalite occurs as intergrowths with bismuthinite,krupkaite, and aikinite or with galena in quartz (Fig. 6f–g,
j–k). It forms needle-like crystals up to 300 µm long. The
empirical formula for studied cosalite based on 20 anions(Topa and Makovicky 2010) can be expressed as (Cu0.87–1.33
Ag 0.19–0.38 ) Σ1.06–1.63 (Pb 6.93–7.45 Fe 0.00–0.27 ) Σ6.93–7.63 (Bi 7.57–8.19
Sb0.08–0.21)Σ7.73–8.28SΣ20. Following the general formula forcosalite (CuxAgi+sPb8–2s–0.5(x+i)Bi8+sS20) proposed by Topaand Makovicky (2010), cosalite from Kizhnica is characterized by mainly 2(Cu+ + Ag+) ↔ Pb2+ substitution, whereparameter x (the content of Cu) is in the range from 0.87
up to 1.33 (Fig. 10a). Silver is partially involved in substitution with Cu, and parameter i is in the range from0.01 up to 0.38. Additionally, substitution Ag+ + Bi3+ ↔
2Pb2+ (“lillianite” type of substitution) is presented in a
low degree – the content of silver (s) is in the range from0.02 up to 0.26 apfu (Fig. 10b). The content of trivalentMineralogical and geochemical studies of Cu–Bi–Ag±W ores from Janjevo (Kosovo)

105
100
95
90

Aikinite8580Friedrichite

75
70

naik (aikinite mol. %)elements (Bi + Sb + As) is close to the ideal number 8 apfu
(in the range 7.73–8.28), showing limited substitution of
Ag for Bi. The Sb3+ ↔ Bi3+ substitution is not significant– the concentration of Sb is up to 0.21 apfu in cosalite
from the Janjevo (Fig. 10c).
There are two generations of bournonite in the samples from Janjevo (Fig. 4). Bournonite I forms irregularinclusions up to 50 µm within galena I aggregate. The
younger generation of bournonite II occurs as irregularaggregates within tetrahedrite grains (Fig. 6l). The chemical formula of bournonite is Pb1.01–1.05Cu1.03–1.06(Sb0.61–0.85
As0.07–0.30)Σ0.90–0.93SΣ2.91–3.10. Bournonite from Janjevo exhibits enrichment in As (bournonite-seligmannite solid
solution). The BSE images reflect an outer rim that is themost As-rich (0.3 apfu) (Fig. 6l).
Gustavite is a rare sulfosalt in the Janjevo ores. It
usually forms lath-like crystals intergrowing with aikinite
and krupkaite (Fig. 11a). It is partially replaced by an
unknown phase (AgCuBiS3) and younger pearceite (Fig.
11d–e). Gustavite from Janjevo has an average calculated
chemical N = 3.9 (from 3.84 up to 4.06), and the averagevalue of parameter x of AgBi substitution is 0.90, whichis in good agreement with the highly substituted memberof lillianite–gustavite solid solution. Number N (ordernumber for lillianite homologues) was calculated using
the formulae N= –1 + 1/(Bii + Pbi/2–1/2) and x = (mol%NAgBiL)*(N–2)/200, where we must firstly normalize
analyses via Ag + Pb + Bi = 1, proposed by Makovicky
and Karup-Møller (1977). Simultaneously Cu and Fe
contents should be ignored. The chemical formula ofgustavite from Janjevo is (Ag 0.86–0.91Cu 0.09–0.21Pb 1.07–1.12
Fe0.01–0.04Bi2.69–2.83)Σ5SΣ5.73–6.01. The concentrations of Cu
and Fe measured with microprobe were likely affectedby associated tetrahedrite and chalcopyrite. Calculationsof numbers N, where Cu was added to the Ag, gave theaverage number N = 4.87 and where Cu was subtracted
by Cu+ + Pb2+ ↔ Bi3+ + □ substitution gave the average
number N = 3.36. In both cases, N is away from the real
known lillianite homologues (4 or 5.5).
Members of pearceite–polybasite group are observedin paragenesis with Cu–Bi ± Ag ± As sulfosalts in the orefrom Janjevo. They are represented by the As-members:
pearceite and cupropearceite. They form irregular aggregates or grains overgrowing Bi sulfosalts and replacetetrahedrite group minerals (Fig. 11b–e). The size of thegrains or aggregates is up to a few hundred µm. The general formula of the pearceite-polybasite group minerals is[M6T2S7][Ag9CuS4], where M = Ag, Cu, and T = As, Sb(Bindi et al. 2007a, b). Minerals of this group have two
pseudo-layer modules: a [M6T2S7]2– A module layer anda [Ag9CuS4]2+ B module layer (Bindi et al. 2007a). Pearceite–cupropearceite from Janjevo has variable Ag and
Cu contents, with Ag varying between 11.37 and 13.21
apfu and Cu content between 2.81 and 4.65 apfu. Analy-

65

Hammarite
EmiliteLindströmite

60
55

Krupkaite

50
45
40
35
30
25

PaariteSalzburgite
GladiteJanjevo Cu-Bi-Ag(W) (this study)
Kizhnica Quarry Cu-Bi (Mederski et al. 2021a)
Kizhnica Hornfels Bi-Au-Cu-Te(Mederski et al. 2021a)

20
Pekoite15
10
5

Bismuthinite

0Fig. 8 – Position of the species of the bismuthinite–aikinite series fromthe Janjevo area determined by their naik after Topa et al. (2002).

ses that show a predominance of Cu (> 3 apfu) within
the A module layer [M6T2S7]2–, represent the Cu-dominant
member: cupropearceite (Fig. 12), according to the classification by Bindi et al. (2007a, b). Additionally, Sb
content is neglectable, and the maximum content of Sb is0.09 apfu. Pearceite is slightly enriched in Bi with maximum content of 0.19 apfu. These higher Bi concentrations are attributed to Bi-sulfosalts replaced by pearceite.
Contents of other elements, such as Fe and Pb are low
and reach a maximum of 0.04 apfu for Pb and 0.44 for Fe.
The chemical formula for pearceite from Janjevo (basedon sum of 18 cations) is [(Ag 2.99–4.21Cu 1.81–2.93Fe 0.09–0.44
Pb0.00–0.04)6.19–6.29(As1.69–1.80Bi0.01–0.04Sb0.00–0.01)1.71–1.81S6.69–7.04][Ag9CuS4], while for cupropearceite is [(Ag2.37–3.00Cu3.08–3.65
149

Sławomir Mederski, Jaroslav Pršek, Joanna Kołodziejczyk, Konrad Kluza, Vasilios Melfos, Katarzyna Adamek, Dimitrina Dimitrova

Janjevo Cu-Bi-Ag(W) (this study)
Kizhnica Quarry Cu-Bi(Mederski et al. 2021a)
Kizhnica Hornfels Bi-Au-Cu-Te(Mederski et al. 2021a)
Stan Terg(Kołodziejczyk et al. 2015; 2017)
Ideal composition

Bi+Sb
Bismuthinite

Galenobismutite
Gustavite

MatilditeCannizzarite
Cosalite
Lillianite

AgCuBiS3
Wittichenite

Cu+Ag
Fe0.06–0.34Pb0.00–0.02)6.14–6.29(As1.52–1.80Bi0.00–0.19Sb0.00–0.09)1.71–1.86
S6.84–7.10][Ag9CuS4].
Wittichenite is a rare phase at Janjevo. It occasionally occurs in small aggregates with other Bi sulfosalts –mainly aikinite and gustavite. The cation/anion ratio is 4 :3, the same as in stoichiometric wittichenite composition.
Chemically it is Ag – enriched and the content of Ag is up
to 0.4 apfu (Tab. S3; Fig. 13). The formula of wittichenite
calculated on the base of 4 cations could be written as:
Cu2.55–2.73Ag0.12–0.39Fe0.02–0.07Sb0.05–0.06Bi0.93–1.04S2.90–3.12.
The unknown phase with a general composition of
AgCuBiS3 is very rare at the locality. It is associated withother Bi sulfosalts like aikinite, krupkaite, wittichenite,
and gustavite, as well as with tetrahedrite and pearceite.
It commonly occurs between older gustavite/aikinite
and younger pearceite, forming aggregates up to 10 µm(Fig. 11d–e). Chemical composition is stable, including
Ag, Cu, Bi, and S as the main elements (Tab. S3, ESM3;
Fig. 13). The calculated cation/anion ratio is 3 : 3. This
unknown phase could be compared with Cu-rich membersof pavonite homologues. However, microprobe analyses
have not detected Pb in sufficient concentrations, whichis required for this group of minerals (Karup-Møller and
Makovicky 1979; Moëlo et al. 2008; Topa et al. 2012).
The chemical composition of the unknown phase is close
to Ag-rich wittichenite. However, the cation/anion ratioof the unknown phase 3 : 3 (or 4 : 4) does not match the
4 : 3 ratio in the theoretical wittichenite composition
Cu3BiS3 (calculated on the base of 4 cations). The formula of the unknown phase, calculated on the base of150

Heyrovskýite

Pb

Fig. 9 – Ternary plot Cu+Ag vs. Bi+Sb
vs. Pb of bismuth sulfosalts from the
Janjevo, Kizhnica and the Stan Terg
area (Kołodziejczyk et al. 2015, 2017;
Mederski et al. 2021a).

3 cations, could be written as: Cu0.92–1.05Ag0.96–1.09Fe0.00–0.04
Sb0.01–0.04Pb0.00–0.04Bi0.9–0.98S2.72–3.00.

5.2.4. Other minerals
In addition, there is wolframite in the ore from Janjevo,
which is represented by members of the ferberite–hübnerite series. Wolframite co-crystallized with quartz(Fig. 11f). It forms euhedral crystals up to 2 mm (Fig. 3f,
11g–h). Wolframite from Janjevo is characterized by atransitional chemical composition with variable Fe andMn contents: (Fe0.50–0.80Mn0.23–0.54Ti0.00–0.02Ca0.00–0.02)Σ1.03–1.07[WO4]0.97–0.99. Most of the chemical analyses plot in theclassification field of ferberite, with only one analysis indicating hübnerite. Its position in the paragenetic sequence of
Cu–Bi–Ag ± W mineralization at Janjevo is not confirmed,
and further studies are needed to determine the formation
conditions. The potential epithermal origin of the Janjevo
wolframite known from only a few locations in the world
cannot be excluded (e.g., Kalinaj 1992; Milési et al. 1994;
Bailly et al. 2002; Damian et al. 2016; Wagner et al. 2005;
Skoupras et al. 2022).
Native bismuth is co-crystallized with arsenopyrite I
and löllingite (Fig. 4). It occurs as irregular blebs up to
50 µm within aggregates of arsenopyrite I and löllingite(Fig. 5i–j). In addition, disseminated native bismuth crystals are observed within quartz and siderite. The analyzed
droplets are chemically homogeneous, with small admixtures of Fe (up to 1.46 wt. %) and Sb (up to 0.32 wt. %),attributed to contamination of arsenopyrite and löllingite.

Mineralogical and geochemical studies of Cu–Bi–Ag±W ores from Janjevo (Kosovo)

5

9.6

(a)

(b)
Scharecck

Scharecck

9.2

4

8.8
3

Ag+Bi [apfu]

2(Cu+Ag) [apfu]

Altenberg 1

Erzwiess
Ocna de Fier
Altenberg 1

2

Erzwiess

Felbertal

8.4

Baia Sprie

Baia Sprie

Habachtal
Ocna de Fier

8

RudnikRudnikFelbertal

1

Habachtal 7.6
Kram
Kram
7.2

0
6

6.4

6.8

2.4

7.2
Pb [apfu]

(c)

7.6

8

Scharecck

Cu+Ag [apfu]

Erzwiess
Altenberg 1

1.2

Ocna de Fier
Baia Sprie

0.8

RudnikHabachtal

0.4

13

14
2Pb [apfu]

15

16

Janjevo Cu-Bi-Ag(W) (this study)
Kizhnica Quarry (Mederski et al. 2021a)
Kizhnica Hornfels (Mederski et al. 2021a)
Stanos - Chalkidiki (Voudouris et al. 2013)
Stan Terg (Kołodziejczyk et al. 2017)
Mazhiq (Mederski et al. 2018; Węgrzynowicz et al. 2019)
Mazhiq Panorama (Węgrzynowicz et al. 2019)
Other localities:
 Boranja - Kram (Radosavljević-Mihajlović et al. 2007) Felbertal (Topa and Makovicky 2010)
 Habachtal (Topa and Makovicky 2010)
 Altenberg 1 (Topa and Makovicky 2010)
 Ocna de Fier (Topa and Makovicky 2010)
 Erzwiess (Topa and Makovicky 2010)
 Scharecck (Topa and Makovicky 2010)
 Rudnik (Stojanović et al. 2006)
 Baia Sprie (Buzatu et al. 2015)

2

1.6

12

Kram
Felbertal

0
7.2

7.6

8
Bi+Sb [apfu]

8.4

8.8

Fig. 10 – Binary plots showing the chemical composition of cosalite from the Janjevo area and known locations of cosalite from the literature (Stojanović
et al. 2006; Radosavljević-Mihajlović et al. 2007; Topa and Makovicky 2010; Voudouris et al. 2013; Buzatu et al. 2015; Kołodziejczyk et al. 2017;
Mederski et al. 2018, 2021a; Węgrzynowicz et al. 2019). a – 2(Cu + Ag) vs. Pb (apfu). b – Ag + Bi vs. 2Pb (apfu). c – Cu + Ag vs. Bi + Sb (apfu).

Siderite is the main component of the Janjevo veins.
It crystallized during the early base metal stage, the mainstage, and the late stage (Fig. 4). It forms coarse-crystalline
aggregates with grains up to several cm (Fig. 3a–c). BSE
images show oscillatory zonation (Fig. 11i), caused byvariations in chemical composition, where Fe is being substituted not only by Mn, but also by Mg and Ca. The formula of siderite is (Fe0.56–0.83Mn0.14–0.38Mg0.01–0.07Ca0.00–0.03)Σ1.00
CO3. Siderite from Janjevo was affected by weathering,with numerous cracks in the crystals or at the grain contacts, filled and replaced by Fe hydroxides (Fig. 11i).

Quartz is ubiquitous in the ore from Janjevo. It crystallized during all hydrothermal stages of precipitation(Fig. 4). It is the main vein-forming mineral of the bismuth stage and co-crystallized with Bi sulfosalts (Fig. 3e;
6f–g, j–k).

5.3. Minor and trace elements in main ore
minerals
Minor- and trace-elements analyses of pyrite, sphalerite,
chalcopyrite, arsenopyrite, and tetrahedrite group miner151

Sławomir Mederski, Jaroslav Pršek, Joanna Kołodziejczyk, Konrad Kluza, Vasilios Melfos, Katarzyna Adamek, Dimitrina Dimitrova

(a)

(c)

(b) Ttr-Tnt III

Krp

Ttr-Tnt III

Aik

Gus

Pea-Cpea
Pea-Cpea

20 μm

(d)

Aik-Gus

(e)

20 μm

Ttr-Tnt III
Aik-Gus

Gn IV

20 μm

(f)
Apy
Feb

unknown phase
AgCuBiS3

Ttr-tnt III

(g)

Qz

Pea-Cpea

Pea-Cpea

Ccp
unknown phase
AgCuBiS3

20 μm

20 μm

(h)

Gn

Ttr-Tnt III

Ccp III

250 μm

(i)
Feb

Feb
Feb
100 μm

250 μm500 μmFig. 11 – Reflected-light photomicrographs (f) and back-scattered electron (BSE) images (a–e, g–i) of Cu–Bi–Ag ± W mineralization from the
Janjevo. a – Gustavite–krupkaite aggregate. b – Pearceite–cupropearceite crystals associated with aikinite and tetrahedrite–tennantite. c – Pearceite–cupropearceite crystals associated with tetrahedrite–tennantite, and galena IV. d – Pearceite–cupropearceite crystals growing on older aikinite–gustavite aggregates and reaction rims with crystallized unknown phase AgCuBiS 3. e – Reaction rings of unknown phase AgCuBiS3 between
pearceite–cupropearceite crystals and aikinite–gustavite aggregates, older tetrahedrite–tennantite–chalcopyrite aggregates. f – Euhedral wolframite(ferberite) crystals associated with quartz and tetrahedrite–tennantite–chalcopyrite III–arsenopyrite aggregates. g – Euhedral wolframite (ferberite)
crystals, galena aggregates. h – Assemblages of euhedral wolframite (ferberite) crystals. i – Crystals of zonal siderite with supergene Fe hydroxides crystallized in cracks. AgCuBiS3 – unknown phase AgCuBiS3, Aik – aikinite, Apy – arsenopyrite, Ccp – chalcopyrite, Cpea – cupropearceite,
Feb – ferberite, FeOOH – Fe hydroxides, Gn – galena, Gus – gustavite, Krp – krupkaite, Pea – pearceite, Qz – quartz, Sd – siderite, Tnt – tennantite, Ttr – tetrahedrite.

als from Janjevo have been obtained from LA-ICP-MSand are presented in Tab. S4 (ESM 4). Additionally,
Fig. 14 shows box plot diagrams of minor and traceelements in the studied minerals, where median, firstquartile, third quartile, 5th percentile, 95th percentile, andoutliers are indicated. The minerals mentioned above,
which are sufficiently large and free of major inclusions
and irregular intergrowths with other mineral phases,
were used for studies using LA-ICP-MS. Therefore,
minerals from the early base metal stage (pyrite andsphalerite I), bismuth stage (arsenopyrite I), and the mainstage (sphalerite II, chalcopyrite III, arsenopyrite II, and152

tetrahedrite group minerals) were selected for measurements. Representative time-resolved LA-ICP-MS depth
profiles of studied ore minerals are presented in Fig. 15
and 16.
Pyrite is characterized by variable concentrations ofAs (up to 26,565 ppm, median: 14,769 ppm), significant
contents of Ni (median: 662 ppm) and Co (median: 38.9ppm) (Tab. S4). In addition, some analyses showed elevated concentrations of Au (up to 7.20 ppm, median:
2.27 ppm) and Te (up to 13.35 ppm).
In the ore from Janjevo, two generations of sphalerite
are distinguished, which differ in their trace element con-

Mineralogical and geochemical studies of Cu–Bi–Ag±W ores from Janjevo (Kosovo)

27.84 ppm) (Tab. S4; Fig. 15c). Tin and indium seemto be increased together in some zones (Fig 15d). The
medians of other trace elements in chalcopyrite III are as
follows: Cd (6.82 ppm), Ge (2.07 ppm), Ag (1.87 ppm),
and Bi (1.42 ppm).
Antimony and bismuth are the main trace elements
occurring in the structure of arsenopyrite from Janjevo.
Arsenopyrite I is characterized by high concentrationsof Sb (median: 15,483 ppm) and Bi (median: 3,383ppm), while arsenopyrite II shows lower contents of Sb(median: 9,892 ppm) and Bi (median: 196 ppm) (Tab.
S4). These elements in arsenopyrite I are incorporated
either in the lattice of the mineral or in nano-inclusions,as suggested by the flat LA-ICP-MS spectra (Fig. 15e);moreover, analyses of arsenopyrite I were conductedon crystals without visible native Bi micro-inclusions(Fig. 6c). Other trace elements occurring in significant
amounts are Cu (median: 603 ppm), and Pb (median: 455ppm), which are the result of sulfide inclusions.
The tetrahedrite group minerals (TGM) can incorporate a wide range of major and trace elements. Minerals
from this group occurring in the Janjevo ore form a solid
solution with transitional chemistry from tetrahedriteto tennantite. For describing the trace elements, thepopulation was divided into two groups: tetrahedrite andtennantite (Fig. 16a–c). Silver occurs in minor amounts
in the TGM from Janjevo: the median Ag content in
the tetrahedrite is 14,751 ppm and in the tennantite 940

5[(Ag,Cu)6As2S7][Ag9CuS4][Ag-9] [apfu]

4
pearceite

3

cupropearceite

2
1.5

2

2.5
3
[Cu-1] [apfu]

3.5

4Fig. 12 – Cu-1 vs. Ag-9 binary plot (apfu) of pearceite–cupropearceitefrom the Janjevo (Bindi et al. 2007a).

tent. Sphalerite I is characterized by significantly higher
Fe and Mn contents (medians: 29,817 ppm of Fe; 178
ppm of Mn), while sphalerite II contains 2,844 ppm Fe
and 8.73 ppm Mn (medians). The medians of other traceelements in sphalerite are as follows and are higher for
sphalerite I: Cu (I – 395 ppm, II – 387 ppm), In (I – 23.73
ppm, II – 3.05 ppm), Sn (I –21.81 ppm, II – 6.07 ppm), Ga(I – 8.46 ppm, II – 6.77 ppm),
Ge (I – 9.15 ppm, II – 3.9 ppm)
(Tab. S4). On the other hand,higher Cd and Hg contents areobserved in sphalerite II: for
Cd (medians: I – 1,458 ppm, II– 2,782 ppm) and Hg (medians:
I – 20.43 ppm, II – 38.39 ppm).
Janjevo AgCuBiS (this study)
Interestingly, only sphalerite II
Janjevo wittichenite (this study)
Aktash deposit
shows a signal of Bi (median(Yatimov et al. 2019)21.43 ppm), while the LA-ICPIdeal composition
MS spectrum show a homogenous distribution (Fig. 15c).
The main trace elements
present in chalcopyrite III are
Phase XZn (median: 807 ppm), In (up to
AgCuBiS
142 ppm, median: 72.39 ppm),
Sn (up to 158 ppm, median:
10.30 ppm), and Mn (median:
3

Ag

Arcubisite
Ag6CuBiS4

3

Fig. 13 – Ternary plot Cu vs. Ag vs. Biof unknown phase (AgCuBiS3) and wittichenite from the Janjevo and Aktash
deposits (Yatimov et al. 2019).

Cuprobismutite
Cu8AgBi13S24

Bi

Hodrušite
Cu8Bi12S22
Emplectite
CuBiS2

Wittichenite
Cu3BiS3Cu
153

[ppm]

Sławomir Mederski, Jaroslav Pršek, Joanna Kołodziejczyk, Konrad Kluza, Vasilios Melfos, Katarzyna Adamek, Dimitrina Dimitrova

10

6

10

5

10

4

103
10

2

10

1

10

0

10-1
106

Mn

Fe

Co

Ni

Cu

Zn

Ga

Ge

As

Ag

Cd

In

105

[ppm]

104
103
102
101
100
10-1
106

outliers
10

5

10

4

10

3

95th percentile[ppm]

third quartile
medianfirst quartile

5th percentile

102
101
100
10-1

Sn

Sb

Hg

Pb

Bi

Arsenopyrite
Chalcopyrite
PyriteSphalerite
TetrahedriteGroup Minerals

Fig. 14 – Box plot showing minor and trace element concentrations [in ppm] measured by LA-ICP-MS in arsenopyrite, chalcopyrite, pyrite, sphalerite, and tetrahedrite group minerals from the Janjevo Cu–Bi–Ag ± W mineralization.

ppm. The medians of the divalent trace elements present
at the C position in the tetrahedrite structure are: 371
ppm Cd, 16.40 ppm Hg, 11.54 Mn, and 5.25 ppm Pb.
154

The concentrations in tennantite are 65.5 ppm Cd, 57.33
ppm Hg, 8.84 ppm Mn, and 630 ppm Pb, respectively.
The trivalent In medians are similar in both TGM, 38.95

Mineralogical and geochemical studies of Cu–Bi–Ag±W ores from Janjevo (Kosovo)

ppm in tetrahedrite, and 36.69 ppm in tennantite. In addition, tennantite shows significantly higher Ge, Sn, and Tl
concentrations (the medians are respectively 16.89 ppm,
30.33 ppm, and 5.8 ppm). In tetrahedrite the Ge concentrations are 5.21 ppm (median), while Sn and Tl are
below the detection limit. Other trace element contents in
TGM (Ga, Mo, Se, and Te) are in most of analyzed spots
below detection limits.

6. Discussion

10

(a)

galenacounts

104

10

3

10

2

(b)

107
[ppm]
As 12,190
Pb 42.29
Sb 9.52
Au 2.27
Ag 0.12

105

8

Py
10

Sph I
[ppm]
Fe 32,503
Cd 3,443
Cu 530
Sb 360In 36.76
Ag 27.00
Hg 14.27
Sn 13.35

6

105
104
103
102

101
0
10

40

8

107

80
time (s)

(c)

101

160

0

40

[ppm]
Cd 2,782
Cu 330Pb 43.64
Bi 33.18
Sb 22.76
Ag 12.44

105
104

57

118

Sn

65

121

Sb

66

Zn

197

Au

As

202

Hg

Ag

208

Pb

209

Bi

Fe
Cu

75

107

103

111

Cd

10

2

115

In

10

1

0

107
10

6

40

80
time (s)

(d)

120

[ppm]
Cu 424,604
Zn 347
In 26.68
Sn 10.30
Bi 0.39
Pb <bdl

4

107
10

6

160

102

102

80
time (s)

120

160

[ppm]
As 414,760
Sb 16,815
Bi 2,160
Cu 513
Pb 233Ag 7.01

104
103

40

Apy I

(e)

105

103

101
0

120

160

Ccp III

105
10

80
time (s)Sph II106

counts120

countsFig. 15 – Representative time-resolved
laser ablation ICP-MS depth profilesof sphalerite, chalcopyrite, and arsenopyrite from the Janjevo Cu–Bi–Ag ± W
mineralization. The contents of individual elements shown on the graphs referto the specific measurement locations
presented on the time-resolved laser
ablation ICP-MS depth profiles (a–e).
a – Pyrite. b – Sphalerite I. c – Sphalerite II. d – Chalcopyrite III with zones
enriched in In and Sn. e – Arsenopyrite I.

7106counts

Bi–Pb ± Cu ± Ag and Cu–
Bi ± Ag ± As sulfosalts are typically the primary carriers ofBi and Ag in the Cu–Bi zones
of deeper hydrothermal deposits associated with volcanic
rocks (Ciobanu and Cook 2000;
Stojanović et al. 2006; Jeleň etal. 2012; Buzatu et al. 2015;
Kołodziejczyk et al. 2015; Mederski et al. 2021a). There are
two main sulfosalt parageneses
in Janjevo: Bi–Pb ± Cu ± Ag
and Cu–Bi ± Ag ± As paragenesis (Fig. 4). The first paragenesis is represented by bismuthinite, aikinite, krupkaite,
cosalite, and gustavite, while
the second includes pearceite,
cupropearceite, wittichenite,and unknown phase: AgCuBiS3(Fig. 4).
The Bi–Pb ± Cu ± Ag paragenesis is relatively common
in hydrothermal deposits from
Vardar Zone (Stojanović et al.
2006, 2018; Radosavljević-

10

counts

6.1. Sulfosalt mineralparagenesis andsubstitution trends

Mihajlović et al. 2007; Voudouris et al. 2008, 2013,2018; Radosavljević et al. 2013; Budinov et al. 2015),
especially in the Trepça Mineral Belt in Kosovo(Kołodziejczyk et al. 2015, 2017; Mederski et al. 2018,2021a; Węgrzynowicz et al. 2019). The characteristic
mineral of this paragenesis is cosalite, which, dependingon genetic types of the mineralization and the nature of
the fluids, shows considerable chemical variability. The
substitutions observed in cosalite are: 2(Cu+ + Ag+) ↔ Pb2+
(Fig. 10a), Ag+ + Bi3+ ↔ 2Pb2+ “lillianite” type of substitution (Fig. 10b), or Sb3+ ↔ Bi3+. A similar type of
substitutions is observed in samples from Ocna de Fier

101

0

40

80
time (s)

120

160

155

Sławomir Mederski, Jaroslav Pršek, Joanna Kołodziejczyk, Konrad Kluza, Vasilios Melfos, Katarzyna Adamek, Dimitrina Dimitrova

Cu–Fe skarn (Topa and Makovicky 2010) and epithermal
Cu–Bi veins in Trepça Mineral Belt: Kizhnica quarry and
Mazhiq (Mederski et al. 2018, 2021a; Węgrzynowicz etal. 2019) (Fig. 10a–c). On the other hand, completely
different trends are shown in cosalite from skarn localities known in the Serbo-Macedonian metallogenic province (Rudnik, Kram, Stan Terg, and Kizhnica hornfels)(Stojanović et al. 2006; Radosavljević-Mihajlović et al.
2007; Kołodziejczyk et al. 2017; Mederski et al. 2021a).
In the Bi–Pb ± Cu ± Ag paragenesis, bismuthinite-aikinite
series members are also very common, usually dominated by bismuthinite and krupkaite, while aikinite isan accessory mineral. On the other hand, in the Janjevo
copper ore, aikinite is one of the main Bi sulfosalts. In
addition, characteristic exsolutions of various membersof the bismuthinite-aikinite series are absent from known
locations in the Vardar Zone. Such exsolutions originate
from primary phases, which crystallize at temperatures
over 300 °C (Springer 1971) and are known from, e.g.,the Ocna de Fier Cu–Fe skarn deposit (Ciobanu and Cook
2000) or the Felbertal W deposit (Topa et al. 2002, 2008).
Mineral paragenesis, in which Cu–Bi ± Ag ± As sulfosalts are the major minerals, is considerably rare. This
paragenesis is commonly associated with intrusive magmatic rocks, including porphyry systems: hydrothermalveins (Jeleň et al. 2012; Izumino et al. 2014; Voudouris
108

(a)
10

108

Ttr III

7

counts

105
10

4

10

3

102

107

40

80
time (s)(c)

counts

4

103
102

156

120

160

[ppm]
As 213,068
Zn 50,306
Fe 38,267
Sb 1,815
Pb 1,265
Ag 558
Cd 51.01
In 43.67
Hg 32.73
Sn 25.13
Bi <bdl

105

101
0

5

104
103

101
0

40

Tnt-Ttr III

106

10

10

102

101
0
108

(b)

106

counts[ppm]
As 198,709
Sb 43,750
Zn 53,600
Fe 33,526
Bi 2,861
Ag 2,424
Cd 277
Hg 115
In 43.69

106

107

40

80
time (s)120160

et al. 2022), skarns (Ciobanu and Cook 2000; Ilinca
2006; Yatimov et al. 2019; Tămaș and Andrii 2020), andcarbonate-replacements (Voudouris et al. 2008). It is typical for Cu–Bi ± Ag ± As paragenesis to be represented bycomplex mineralogy with sulfosalts, such as membersof the cuprobismutite series and pavonite homologous
series, emplectite, wittichenite, and occasionally pearceite, enargite, or luzonite. In the Janjevo occurrence,
sulfosalts with Pb did not crystallize during the formationof the above paragenesis, because Pb was incorporated
into Ag–Bi-rich galena at that stage. Relatively common
in the Janjevo paragenesis are pearceite and cupropearceite. Pearceite is widespread in many hydrothermal
deposits elsewhere in the world (e.g., Voudouris et al.
2022), while cupropearceite is rare and known only froma few locations (e.g., Bindi et al. 2007b, 2015; Bindi and
Pekov 2009; Sejkora et al. 2010; Kozub-Budzyń andPiestrzyński 2018). However, we observe a continuous
variation in Ag and Cu concentrations on the A module
layer [M 6T 2S 7] 2 in pearceite–cupropearceite members
from Janjevo, while both members in one paragenesis
in the world are rare. Experimental studies by Harlov
and Sack (1994) indicate that the widest Cu–Ag substitutional range is observed in the temperatures 75 °C
and 150 °C, which is similar to data from Janjevo, where
we observe a variation in Cu content from 8.5 to 14.5
wt. %. Another unique mineralin Janjevo is the unknown phase– AgCuBiS3. It was formed in
Tnt IIIreaction zones between pearceite–cupropearceite and older[ppm]
As 225,108
gustavite/ aikinite aggregates.
Fe 55,807
A mineral of similar chemical
Zn 15,517
composition is described in
Sb 5,711
Pb 2,046
the Aktash deposit by Yatimov
Ag 1,093
et al. (2019). Yatimov et al.
Hg 101(2019) identified this phase as
Cd 24.76
In 12.91
Ag-bearing wittichenite, and it
Bi 2.94
occurs in a paragenesis similar
to Janjevo – members of the
80
120
160
bismuthinite–aikinite series,
time (s)wittichenite, emplectite, andgalenobismutite. Recalculating
the chemical analyses of this

57

115

In

65

118

Sn

66

Zn

121

Sb

As

202

Hg

107

Ag

208

Pb

111

Cd

209

Bi

Fe
Cu

75

Fig. 16 – Representative time-resolved
laser ablation ICP-MS depth profilesof tetrahedrite group minerals from the
Janjevo Cu–Bi–Ag ± W mineralization.
The contents of individual elements
shown on the graphs refer to the specificmeasurement locations presented on thetime-resolved laser ablation ICP-MS
depth profiles (a–c). a – Tetrahedrite
III. b – Tennantite III. c – A transitionzone between tennantite III and tetrahedrite III.

Mineralogical and geochemical studies of Cu–Bi–Ag±W ores from Janjevo (Kosovo)mineral from Aktash based on 3 cations gives the following empirical formula: Cu0.99–1.01Ag0.98–1.18Fe0.00–0.08Bi0.83–0.93
S2.85–3.00, which is close to the empirical formula of theunknown phase AgCuBiS 3 from Janjevo. In addition,
the compilation of data from Aktash and Janjevo in a
ternary plot Cu vs. Ag vs. Bi indicates a similar chemicalcomposition and highlights a high homogeneity of the
AgCuBiS3 mineral from Janjevo (Fig. 13).

6.2. Trace elements distribution
The complexity of the Cu–Bi–Ag ± W mineralizationfrom Janjevo, in addition to the presence of many sulfosalts, is manifested by the presence of several generations of base metal sulfides (BMS), which could be
distinguished due to textural features as well as traceelements (Fig. 4). Trace elements from the order of a few
ppm to tens of thousands of ppm were measured by laser
ablation inductively-coupled plasma mass spectrometry(LA-ICP-MS). The method is widely applicable to manyore minerals from various genetic types and many studies
have been published over the past 20 years: sphalerite(e.g., Cook et al. 2009; Frenzel et al. 2016), pyrite (e.g.,
Large et al. 2009; Wang et al. 2021), chalcopyrite (e.g.,
George et al. 2018; Foltyn et al. 2022), and arsenopyrite(e.g., Lee et al. 2019; Gourcerol et al. 2020). However,despite the widespread occurrence of tetrahedrite groupminerals (TGM) in hydrothermal environments, only a
few works address the issue of trace elements in TGM(George et al. 2017; Sitarz et al. 2021; Silyanov et al.
2022). Moreover, studies of the partitioning of trace elements in sphalerite + galena + chalcopyrite (± tetrahedrite
group minerals) in hydrothermal ores indicate preferential
trends of individual trace elements and potential cocrystallization (George et al. 2016, 2017). Observationof the time-resolved downhole ablation profiles (Fig.
15a–e; 16a–c) helps distinguish obvious micro-inclusions
in the host mineral (Cook et al. 2016). Furthermore, thesteadiness of LA-ICP-MS profiles may be related to traceelements as solid solutions or the occurrence of homogeneously distributed nano-inclusions.
Bismuth in the Cu–Bi–Ag ± W ore from Janjevo occurs
in the form of numerous sulfosalts, but its significant
concentrations are also found in ore minerals measured
by the LA-ICP-MS technique. Very high Bi contents of
up to 4,600 ppm exhibit arsenopyrite I, which is widelydistributed in the ore. By crystallization of arsenopyrite I
begins the productive stage for bismuth (stage 2) (Fig. 4),
where the ore shows textures of decomposition and crystallization of native Bi inside arsenopyrite I–löllingite
aggregates (Fig. 5i–j). In addition, crystallization of Bi
sulfosalts in Janjevo took place after the formation ofarsenopyrite I (Fig. 4). The incorporation of bismuth into
BMS differs depending on the generation of individual

sulfides (Fig. 14). In general, the bismuth among BMS
is preferentially incorporated into galena co-crystallizing
with other sulfides (George et al. 2015, 2016). Bismuth
measured by microprobe in galena IV ranged up to 9.27
wt. %, and in galena II, up to 2 wt. %. Significantly
less Bi is found in the other minerals analyzed, where
the medians are: 565 ppm for tetrahedrite III, 2.94 ppm
for tennantite, 196 pm for arsenopyrite II, 1.42 ppm forchalcopyrite III, and 21.43 ppm for sphalerite II. The
mild enrichment in Bi in sphalerite II seems unusual,
especially since the LA-ICP-MS spectrum is flat. The
incorporation of bismuth into the sphalerite structure is
unknown in the literature (Cook et al. 2009). The flat LAICP-MS spectrum and the high abundance of Bi-minerals
in the whole paragenesis suggest rather the presence of
homogenously distributed micro- to nano-inclusion of Bi
sulfosalts. Similar patterns are observed for Cu, Pb, Sb,
and Ag so that they can be linked to the nano-iclusions ofsulfosalts together with Bi (Fig. 15b). Elevated Bi content
in sphalerite associated with micro-inclusions is reported
from some metamorphosed sulfide deposits (Lockington
et al. 2014).
Indium is another significant trace element that is present in the entirely of the Kizhnica–Hajvalia–Badovc ore
field, as well as in Cu–Bi–Ag ± W mineralization from
Janjevo (Mederski et al. 2022b). Indium is a critical metal
and the ores from the Kizhnica–Badovc area (epithermalveins and listvenite ores) show considerable economic
potential in the context of elevated indium contents. Indium shows lower concentrations in ore minerals from
Janjevo compared to other occurrences nearby. However,
the geochemical importance of this element is still wellvisible. The main mineral hosting indium in ores from
Kizhnica–Badovc is sphalerite (Mederski et al. 2019,2021a, b), which reaches In concentrations up to several
thousand ppm (3,160 ppm in sphalerite from listvenites
and 1,600 ppm in sphalerite from Cu–Bi veinlets in Kizhnica quarry). Interestingly, sphalerite in Janjevo is not themain mineral hosting indium. Sphalerite I reaches values
up to 108 ppm (median: 23.73 ppm), while sphalerite IIcontains up to 12.09 ppm In (median: 3.05 ppm). Higher
concentrations of In are found in phases co-crystallizing
with sphalerite II: chalcopyrite III (median: 72.39 ppm)
and tetrahedrite–tennantite III (median: 38.94 ppm fortetrahedrite, and 36.68 ppm for tennantite). Previous studies show that, among the other base ore minerals, sphalerite is the most preferred mineral to incorporate In into
the structure (George et al. 2016, 2017). The presence ofindium in sphalerite and chalcopyrite is known in many
genetic types of deposits (e.g., Murakami and Ishihara
2013; Foltyn et al. 2020; Xu et al. 2021; Voudouris et al.
2022), while the presence of this element in tetrahedrite
group minerals is little documented (George et al. 2017).
So far, elevated indium concentrations in tetrahedrite
157

Sławomir Mederski, Jaroslav Pršek, Joanna Kołodziejczyk, Konrad Kluza, Vasilios Melfos, Katarzyna Adamek, Dimitrina Dimitrovagroup minerals have been reported only in two In-rich
deposits: Neves Corvo (Portugal) – 0.15–2.7 wt. %(Gaspar 2002; Carvalho et al. 2018), and Pefka (Greece)– 4.03–6.5 wt. % (Voudouris et al. 2022). High indium
contents are associated with the tennantite series in these
deposits. In the studied tetrahedrite group minerals from
Janjevo, indium concentrations do not depend on As-Sb
substitution and reach similar contents of ~38 ppm.
Sphalerite is the main carrier of such trace elements
as Cd, Hg, Ga, and Ge in the Cu–Bi–Ag ± W ore from
Janjevo (Fig. 14). The concentrations of Ga, Ge, with
In, Fe, and Mn can be used to estimate crystallization
temperatures using GGIMFis geothermometry (Ga,Ge, In, Mn and Fe in sphalerite) proposed by Frenzel
et al. (2016). Sphalerite I from Janjevo crystallized at
220–272 °C, while sphalerite II precipitated at a much
lower temperature: 160–190 °C (Tab. S4, ESM 4). The
crystallization temperatures of the younger sphalerite
generation correspond to the conditions responsible forthe formation of the main-stage mineralization, which
is typical of low-temperature, epithermal systems (i.e.,
Cu–Bi ± Ag ± As sulfosalts). In general, the formation
temperatures of sphalerite at Janjevo coincide with thoseof sphalerite formation from other styles of mineralization in the Kizhnica–Hajvalia–Badovc ore field: Kizhnica
quarry Cu–Bi epithermal veinlets (250–270 °C), Janjevo
polymetallic veinlets (~340 °C), Janjevo Sb–As–Tl–Hg
sediment-hosted mineralization (230–260 °C), Badovc
Pb–Zn–Sb(Ni) listvenite hosted (210–380 °C), Badovc
Pb–Zn–Sb banded vein-type (250–330 °C), and Badovc
Sb vein-type (180–240 °C) (Mederski et al. 2022b). The
geochemistry of sphalerite reflects the zonation within the
KHB ore field: low-Fe sphalerite, including that from thestudy site, is observed within the Bi–Cu ± Au zone (eastern part), while high-Fe sphalerite is mainly observed
within the Pb–Zn–Sb ± Ni zone (central and western part)(Mederski et al. 2022b).

7. Conclusions
A new type of Bi–Cu ± Au mineralization was identified in
the Kizhnica–Hajvalia–Badovc ore field in Vardar Zone –hydrothermal Cu–Bi–Ag ± W mineralization in Janjevo. Bismuth sulfosalts are an important component in Bi–Cu±Au
mineralization. Whereas the Bi–Pb ± Cu ± Ag sulfosalts
paragenesis is widely known in many deposits in the Vardar Zone, the Cu–Bi ± Ag ± As paragenesis is described in
Kosovo and this part of the Vardar Zone for the first time.
Our studies show that in addition to numerous Bi
sulfosalts in Janjevo ores, bismuth has been incorporated
into base metal sulfides and arsenopyrite. In particular,
the main carrier of bismuth is arsenopyrite I, which has
started the crystallization of the bismuth stage.
158

The application of GGIMFis geothermometry (Frenzel
et al. 2016) on sphalerite from Cu–Bi–Ag ± W ore from
Janjevo gives the following sphalerite precipitation temperatures: 220–272 °C for sphalerite I and 160–190 °C for
sphalerite II, consistent with the ore textures indicative of
the polyphasic development of the mineralization.
Acknowledgments. The research was funded by Society of
Economic Geologists Canada Foundation (SEGCF) Student Research Grant 2019 and by AGH statutory grant no.
16.16.140.315. We are grateful to Tomáš Mikuš, Gheorghe Damian, and the anonymous reviewer for comments
and suggestions that helped significantly improve themanuscript. Handling Editor Jiří Sejkora is also thanked
for his efficient handling of the manuscript. We are grateful to Adam Włodek and Gabriela Kozub-Budzyń fromthe Laboratory of Critical Elements at AGH-UST, Facultyof Geology, Geophysics and Environmental Protection,
for their help during EMPA data collection. In addition,
I would like to thank the many AGH students for their
help in the fieldworks. Special thanks for their significant
contribution to the fieldwork goes to Konrad Pytel.
Electronic supplementary material. Complete data forelectron-probe microanalyses of minerals and LA-ICPMS data from Janjevo are available online at the Journal
website (http://dx.doi.org/10.3190/jgeosci.371).

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